Mercerizing assistants



Patented A r. 6, 1937 UNITEDSTATES PATENT OFFICE No Drawing. Application January 30, 1934, Serial No. 708,967

16 Claims.

This invention comprises improvements in I and relates to-the treatment of cellulose or cellulose-like bodies with compounds possessing a swelling action. It is an object of this invention 5 to improve the rate of swelling of cellulose bodies in the presence of alkaline solutions. It is a further object of this invention to obtain higher shrinkage of cellulosic bodies than that usually obtained. It has long been known that phenols or cresols possess a wetting out actionwhen added to alkaline solutions; In British Patent #364,844, it is shown that mixtures of phenols with nitrogen containing organic bases are particularly efiective in speeding up or increasing the wetting out properties of alkaline solutions. It is also shown in French Patent #733,170 that the alcohol sulphates prepared by sulphating alcohols having a boiling range of 120-160 C. are particularly effective wetting agents. British Patent #378,223 covers the use of the ethers of a polyhydricalcohol containing at least two free hydroxyl groups as wetting agents for mercerizing liquors. While these products are of interest, we have found'that they may cause a gradual darkening of alkaline solutions or they may be 1 volatile "in steam and hence lostwhen the alkaline solution is evaporated in order to recover the caustic.

We have found that ether acids or their salts are particularly efiective and greatly accelerate the wetting rate of mercerizing liquors when present in extremely low concentrations. A number of these ether acids have been described by Bruson, U. S. Patents #1,920,137 and #1,920,160. We havefound that the sodium salts of the ether acids are good mercerizing assistants and that the quaternary ammonium V f salts are particularly active and effective in low 40 concentrations. It is evident that the free acid may be added to the mercerizing bath since the I sodium salt would be formedin the bath. Mixtures of the free acid with quaternary ammonium salts may also be added to a 20% sodium hydroxide solution thus forming the quaternary ammonium salt of the ether acid.

The ether-acids employed in the present invention 'have the general formula R'OR COOH in which R is an aliphatic,.aromatic,

arylaliphatic, or hydroaromatic group and R is an aliphatic group or alkylene radical. Generally those acids are best suitedto the purposes of the present invention when the group R contains from two to ten carbon atoms and the group R from one to seven carbon atoms.

Groups containing more than these numbers of carbon atoms may also be-used but the results are not-so satisfactory.- These acids are substantially colorless liquids and their salts may be readily crystallized. The boiling points are 5 very high so they are substantially non-volatile in the mercerizingbath. They have the added properties of being stable in the presence of boiling alkali so that they can be used in cases where the sodium hydroxide is recovered after 10 mercerizing, and of not being decomposed during the concentratin process. Even when heated in alkaline solution these ether acids cause little, if any darkening. The effect of these acids is best shown in the following comparative tests 15 in which cotton-yarn was immersed in mercerizing liquor containing 20% sodium hydroxide at a temperature of 20 to 25 0.:

Rate of shrinkage of cotton yarn immersed in 20% sodium hydroxide with varying ether acids for given periods of time The figures given denotethe shrinkage in per- 35 cent of original length of yarn immersed.

' Other ether acids which have been prepared and found to be of value in assisting the wetting action are the following: heptoxybutyric, ethoxyacetic, n-octyloxyace'tic, cyclohexoxybutyric, 40 amyloxybutyric, heptoxyacetic, xylenoxyacetic,

iscamyloxy'acetic, bornyloxyacetic, benzyloxybutyric, phenoxyacetic, and fi-butoxyethoxyacetic acid. We have also found that mixtures of the ether acids are particularly eifective. These 45 mixtures may be prepared by condensing mixtures of alcohols, prepared synthetically from carbon monoxide and hydrogen, with chlorinesubstituted fatty acids or with unsaturated acids. Alkoxyacetic acids a boiling range of 147-157 C. or with the alcohols boiling from -195 C. are'particularly effective.

' While the ether acids cause a marked im- 55 obtained by condensing 'chloracetic acid with aliphatic alcohols having provement in the wetting action of mercerizing liquors, we have found that mixtures of the ether acids with quaternary ammonium bases or their salts are much more effective than either of them alone and in fact the effect of the mixture is greater than the sum of the individual effects. This may be seen from the following table: I Efiect on rate of shrinkage of cotton yarn in 20% 10 sodium hydroxide solution with additions as given- Time in seconds- I Colman shrinkage after im- 15 Compound added tration on used 15 so 45 so 120 Control-no addition 0.0 1 1.5 a 4 1 0 Octyloxyacetic acid 0.1 5 8 '10 11 13 Trimethylbenzylammonium hydroxide 01 2 4 6 7 9 Trimethylbenzylammonium octyloxyacetate 0.2 15 19 21 22 In addition to the trimethylbenzyl ammonium hydroxide shown in the table, the following quaternary ammonium bases or their salts may also be used:

Dimethylbenzylphenyl ammonium hydroxide, trimethylbenzyl ammonium hydroxide, triethylbenzyl ammonium hydroxide, diethylphenylbenzyl ammonium hydroxide, dimethyltolylbenzyl ammonium hydroxide, dimethylamylbenzyl ammonium hydroxid( dimethyldibenzyl. ammonium hydroxide, trimethylamyl ammonium hydroxide, triethanolbenzyl ammonium hydroxide.

As shown in the tables above, these ether acids act as wetting agents for alkaline solutions and the rate of shrinkage of a cotton yarn gives a direct measure of the rate of wetting. However, in actual plant practice the yarn is treated with alkaline solution under tension so that shrinkage rarely takes place, but the rate of penetration of the alkali into the cotton goods is directly related to the rate of shrinkage, as shown in the above tables. The following examples illustrate the application of these acids:

Example 1.-One hundred-fifty pounds of heptoxyacetic acid is dissolved in 15,0001b. of 21% sodium hydroxide solution. It is thoroughly mixed and 38" cotton broadcloth, after a previ-, ous kier boil, is dried and run thru the mercerizing bath, held out .to width under tension and maintained in the mercerizing bath for60 seconds before washing with water and acid. Fabric treated in this way has an unusually high luster and sheen. 1

Example 2.-One hundred pounds of an aqueous solution containing 20% octyloxyacetic acid and 15 lb. of trimethylbenzylammonium chloride are added to 2000 lb. of 20% sodium hydroxide solution: Cotton yarns previously boiled out to remove the waxes are run into this mixture of caustic, ether acid ,and quaternary ammonium salt, kept in this liquor at 15-20 C. for 2-3 minutes, given a tight squeeze, rinsed, run thru acid and dried to give a yarn of .high'luster and full mercerization.

Example 3.-Five thousand pounds of cotton Example 4.Two thousand pounds-of a mixture of cotton linters and purified wood pulp suitable for rayon manufacture, are wet with an 18% solution of sodium hydroxide containing 1/10 of 1% hexyloxybutyric acid. The cellulose fibers wet out very rapidly in this mixture and there is a rapid swelling.

We have found that these ether acids are particularly effective wetting assistants and can be used generally wherever cellulose bodies are treated with alkaline solutions.

The invention is not limited to the specific materials nor concentrations given in the foregoing examples which are for purposes of illustration any case the addition of small amounts of the ether acid to the alkaline solution greatly increases its rate of wetting. -When the alkali metalhydroxides are used as the mercerizing agent their rate of wetting is increased by the addition of either an ether acid or a quaternary base but not nearly to the same extent as when both are added to the alkaline solution.

In the appended claims, whereit is stated that a quaternary ammonium base is added to the solution, it is understood that a soluble salt of the base may be used in an equivalent amount, because as soon as the salt comes in contact with the strong caustic solution the quaternary ammonium base is set free.

We claim:

1. The process which comprises treating cellulosic materialwith a solution of an alkali metal hydroxide containing a salt of a carboxylic ether acid, said solution being of sufficient strength to exert a mercerizing action.

2; The process which comprises treating ce1lu-.

losic material with a solution of an alkali metal hydroxide containing a salt of a carboxylic ether acid, said solution being of sufficient strength to exert a mercerizing action and a quaternary ammonium base.

3. The process which comprises treating cellu- -losic material with a solution of an alkali metal hydroxide containing a salt of an, ether acid of the formula ROR'COOH, in which R is a hydrocarbon radical containing from two to ten carbon atoms, and R is an aliphatic hydrocarbon radical containing from one toseven carbon matic hydrocarbon radical containing from two losic material with a solution of an alkali metal hydroxide containing a quaternary ammonium base and a salt of an ether acid of the formula R-OR'COOH, in which R is a hydrocarbon radical containing from two to ten carbon atoms, and R is an aliphatic hydrocarbon radical containing from one to seven carbon atoms, said solution being of suflicient strength to exert a mercerizing action. I

8. The process which comprises treating celhas been added from 0.1 to 1.0% of a carboxylic l ether acid.

- 8. The process which comprises treating cellulosic material with a solution containing ap-' 'pr0ximately of sodium hydroxide, to which has been added from 0.1 to 1.0% of an ether acid having the formula R-OR'-COOH, in which R is an aromatic, aliphatic, arylaliphatic or hy droaromatic hydrocarbon radical containing from two to ten carbon atoms, and R is an aliphatic hydrocarbon radical containing from one to seven carbon atoms.

9. The process which comprises treating a cellulosic material with a solution containing approximately 20% of sodium hydroxide to which has been added from 0.1 to 1.0% of a carboxylic ether acid and from 0.1 to 1.0% of a quaternary ammonium base.

g 10. The process which comprises treating a cellulosic material with a solution containing approximately 20% of sodium hydroxideto which 5 has been added from 0.1 to 1.0% of an ether acid having the formula RO--R'COOH in which R is an aromatic, aliphatic, arylaliphatic or hydroaromatic hydrocarbon radical containing from two to ten carbon atoms and R is an ali- '4 0 phatic hydrocarbon radical containing from one to seven carbon atoms, and from 0.1 to 1.0% of a' quaternary ammonium base. '11. Theprocess which comprises treating a cellulosic material with a solution containing approximately 20% of sodium hydroxide to which has been added from 0.1 to 1.0% of heptoxyacetic acid and from 0.1 to,-1.0% of a quaternary ammonium base.

T2. The process which comprises treating a cellulosic material with a solution containing approximately 20% of sodium hydroxide to which has been addedfrom 0.1 to 1.0% of heptoxyacetic acid, and 0.1 to 1.0%.of trimethylbenzyl ammonium hydroxide.

13. The process which comprises treating a cotton fabric under tension with a solution of an alkali metal hydroxide to which has been added a carboxylic ether'acid said solution being of suflicient strength to exert a mercerizing action.

14. The process which comprises treating a cotton fabric under tension with a solution of an alkali metal hydroxide to which has been added a carboxylic ether acid and a quaternary ammonium base said solution being of sufiicient strength to exert a mercerizing action.

15. The process which comprises treating a cotton fabric under tension with a solution containing about 20% of sodiumhydroxide, to-which has been added from 0.1 to 1.0% of an ether acid having the formula R--ORCOOH, in which R is an aliphatic, aromatic, arylaliphatic or hydroaromatic hydrocarbon group containing from two to ten carbon atoms and R is an aliphatic hydrocarbon group containing from one to seven carbon atoms. I

' 16. The process which comprises treating a cotton fabric under tension with a solution containing about 20% of sodium hydroxide, to which has been added from 0.1.to 1.0% of an ether acid having the formula RO--RCOOH, in which, R is an aliphatic, aromatic, arylaliphatic or hydroaromatic hydrocarbon group containing from two to ten carbon atoms and 'R' is an aliphatic hydrocarbon group containing from one to seven carbon atoms and from 0.1 to 1.0% of a quaternary ammonium base.

DONALD H. POWERS.

HAROLD W. STIEGLER. 

